WO1996014052A1 - Method of making polyhydric alcohol solutions of enhanced efficacy antiperspirant actives - Google Patents
Method of making polyhydric alcohol solutions of enhanced efficacy antiperspirant actives Download PDFInfo
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- WO1996014052A1 WO1996014052A1 PCT/US1995/014073 US9514073W WO9614052A1 WO 1996014052 A1 WO1996014052 A1 WO 1996014052A1 US 9514073 W US9514073 W US 9514073W WO 9614052 A1 WO9614052 A1 WO 9614052A1
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- WIPO (PCT)
- Prior art keywords
- solution
- aluminum
- polyhydric alcohol
- enhanced efficacy
- salt
- Prior art date
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- 230000001166 anti-perspirative effect Effects 0.000 title claims abstract description 69
- 239000003213 antiperspirant Substances 0.000 title claims abstract description 69
- 150000005846 sugar alcohols Polymers 0.000 title claims abstract description 64
- 238000004519 manufacturing process Methods 0.000 title description 4
- 150000003839 salts Chemical class 0.000 claims abstract description 84
- 239000000243 solution Substances 0.000 claims abstract description 76
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 48
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000007864 aqueous solution Substances 0.000 claims abstract description 34
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- DHMQDGOQFOQNFH-UHFFFAOYSA-M Aminoacetate Chemical class NCC([O-])=O DHMQDGOQFOQNFH-UHFFFAOYSA-M 0.000 claims abstract description 19
- 238000001704 evaporation Methods 0.000 claims abstract description 16
- 239000012266 salt solution Substances 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 229940071566 zinc glycinate Drugs 0.000 claims abstract description 7
- UOXSXMSTSYWNMH-UHFFFAOYSA-L zinc;2-aminoacetate Chemical compound [Zn+2].NCC([O-])=O.NCC([O-])=O UOXSXMSTSYWNMH-UHFFFAOYSA-L 0.000 claims abstract description 7
- 238000011065 in-situ storage Methods 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 5
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 63
- LVYZJEPLMYTTGH-UHFFFAOYSA-H dialuminum chloride pentahydroxide dihydrate Chemical compound [Cl-].[Al+3].[OH-].[OH-].[Al+3].[OH-].[OH-].[OH-].O.O LVYZJEPLMYTTGH-UHFFFAOYSA-H 0.000 claims description 18
- -1 aluminum-zirconium chlorohydrate Chemical compound 0.000 claims description 17
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 14
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 12
- 150000003754 zirconium Chemical class 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- FMXLGOWFNZLJQK-UHFFFAOYSA-N hypochlorous acid;zirconium Chemical compound [Zr].ClO FMXLGOWFNZLJQK-UHFFFAOYSA-N 0.000 claims description 6
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 5
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 5
- ZGUQGPFMMTZGBQ-UHFFFAOYSA-N [Al].[Al].[Zr] Chemical compound [Al].[Al].[Zr] ZGUQGPFMMTZGBQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000600 sorbitol Substances 0.000 claims description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 4
- 235000013905 glycine and its sodium salt Nutrition 0.000 claims description 4
- 239000004247 glycine and its sodium salt Substances 0.000 claims description 4
- ADGFKRMKSIAMAI-UHFFFAOYSA-L oxygen(2-);zirconium(4+);chloride;hydroxide Chemical compound [OH-].[O-2].[Cl-].[Zr+4] ADGFKRMKSIAMAI-UHFFFAOYSA-L 0.000 claims description 4
- 229940029258 sodium glycinate Drugs 0.000 claims description 4
- WUWHFEHKUQVYLF-UHFFFAOYSA-M sodium;2-aminoacetate Chemical group [Na+].NCC([O-])=O WUWHFEHKUQVYLF-UHFFFAOYSA-M 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 2
- GZWNUORNEQHOAW-UHFFFAOYSA-M potassium;2-aminoacetate Chemical compound [K+].NCC([O-])=O GZWNUORNEQHOAW-UHFFFAOYSA-M 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 4
- 229910052708 sodium Inorganic materials 0.000 abstract description 4
- 239000011734 sodium Substances 0.000 abstract description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052700 potassium Inorganic materials 0.000 abstract description 2
- 239000011591 potassium Substances 0.000 abstract description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 16
- 230000008020 evaporation Effects 0.000 description 12
- 239000004471 Glycine Substances 0.000 description 8
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 8
- 238000007792 addition Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- DNXNYEBMOSARMM-UHFFFAOYSA-N alumane;zirconium Chemical class [AlH3].[Zr] DNXNYEBMOSARMM-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000010561 standard procedure Methods 0.000 description 3
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000003109 Karl Fischer titration Methods 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- AVIYEYCFMVPYST-UHFFFAOYSA-N hexane-1,3-diol Chemical compound CCCC(O)CCO AVIYEYCFMVPYST-UHFFFAOYSA-N 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000012254 powdered material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q15/00—Anti-perspirants or body deodorants
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/26—Aluminium; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/28—Zirconium; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/34—Alcohols
- A61K8/345—Alcohols containing more than one hydroxy group
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
Definitions
- This invention relates to solutions of enhanced efficacy aluminum antiperspirant actives in polyhydric alcohols.
- Enhanced efficacy aluminum and aluminum-zirconium antiperspirant salts are well known and are described, for example, in OB 2,048,229, EP 405,598, US 4,359,456, US 4,775,528, US 4,859,446, US 4,871,525, US 4,900,534, US 4,944,933, US 5,202,115, US 5,234,677, US 5,296,623, and US 5,330,751.
- These enhanced salts are also known to rapidly revert back to their non-enhanced state (for example, as evidenced by an HPLC peak 4 to peak 3 area ratio of 0.3 or less) in solution/ particularly at concentrations greater than 20%. Consequently, the enhanced antiperspirant salts are generally only available in powder form.
- references describe various ways of makin ⁇ alcohol soluble antiperspirant active... These references include, for example, US 3,405,153, US 3,420,932, US 3,523,130, and US 3,947,556.
- concentrated solutions of the antiperspirant active i.e., in the 40 to 50% range
- the product is obtained as a powder, which must then be redissolved in the desired alcohol solution.
- Such techniques pre-date the availability of enhanced efficacy salts and are not believed to be applicable thereto as they would likely cause reversion to the non-enhanced state.
- EP 7191 there is exemplified a process for making a spray dried, powdered complex of enhanced aluminum chlorohydrate and propylene glycol, which complex may then be dissolved in alcohol.
- An object of the present invention is to provide an efficient method for the direct preparation of polyhydric alcohol solutions of enhanced efficacy antiperspirant salts without the need to first isolate the salt as a powder and without any significant loss in efficacy. Such solutions may then be used directly in the preparation of antiperspirant compositions.
- the present invention comprises a process of preparing a solution of an enhanced efficacy aluminum antiperspirant salt in a polyhydric alcohol by
- step (a) requires the preparation of an aqueous solution consisting essentially of about 5% to about 20%, preferably about 8% to about 15%, by weight of an enhanced efficacy aluminum antiperspirant salt in water, the enhanced efficacy aluminum antiperspirant salt having been prepared in situ without having been dried to a solid powder.
- the enhanced efficacy salts when reconstituted as 10% aqueous solutions, produce an HPLC chromatogram (as described, for example, in US 5,330,751, which is incorporated herein by reference) wherein at least 70%, preferably at least 80%, of the aluminum is contained in two successive peaks, conveniently labeled peaks 3 and 4, wherein the ratio of the area under peak 4 to the area under peak 3 is at least 0.5, preferably at least 0.7, and most preferably at least 0.9 or higher.
- the term "enhanced efficacy aluminum antiperspirant salt” is intended to mean a salt which produces such an HPLC chromatogram.
- the preferred aluminum antiperspirant salts are any of the conventional aluminum salts and aluminum-zirconium salts known to be useful in antiperspirant compositions. These salts include aluminum hydroxy halides (e.g., aluminum chlorohydrate) , and mixtures or complexes thereof with zirconyl oxyhalides and zirconyl hydroxyhalides (e.g. aluminum-zirconium chlorohydrate) .
- aluminum hydroxy halides e.g., aluminum chlorohydrate
- zirconyl oxyhalides and zirconyl hydroxyhalides e.g. aluminum-zirconium chlorohydrate
- Preferred aluminum salts are those having the general formula ⁇ l2( H)g_ a X a wherein X is Cl, Br, I or NO3, and a is about 0.3 to about 4, preferably about 1 to 2, such that the ⁇ l to X mole ratio is about 1:1 to 2.1:1. These salts generally have some water of hydration associated with them, typically on the order of 1 to 6 moles per mole of salt. Most preferably, the aluminum salt is aluminum chlorohydrate (i.e. X is Cl) and a is about 1, such that the aluminum to chlorine mole ratio is about 1.9:1 to 2.1:1.
- Preferred aluminum-zirconium salts are mixtures or complexes of the above-described aluminum salts with zirconium salts of the formula ZrO(OH) 2 _ pb Y b wherein Y is Cl, Br, I, N0 3 , or SO4, b is about 0.8 to 2, and p is the valence of Y.
- the zirconium salts also generally have some water of hydration associated with them, typically on the order of 1 to 7 moles per mole of salt.
- the zirconium salt is zirconyl hydroxychloride of the formula ZrO(OH) j . j - j Cl jj wherein b is about 1 to 2, preferably about 1.2 to about 1.9.
- the preferred aluminum-zirconium salts have an Al:Zr ratio of about 1.7 to about 12.5, most preferably about 2 to about 8, and a metal:X+Y ratio of about 0.73 to about 2.1, preferably about 0.9 to 1.5.
- a preferred salt is aluminum- zirconium chlorohydrate (i.e. X and Y are Cl) , which has an Al:Zr ratio of about 2 to about 8 and a metal:C1 ratio of about 0.9 to 2.1.
- Such complexes may also contain a neutral amino acid, preferably glycine, typically with a Zr:Gly ratio of about 1:1 to 1:4.
- a preferred method of preparing aqueous solutions of enhanced efficacy antiperspirant salts comprises heating a 5 to 18% aqueous solution of aluminum salt, preferably aluminum chlorohydrate, at a sufficient temperature and for a sufficient time to provide an HPLC peak 4 to peak 3 area ratio of at least 0.5, preferably at least 0.7, and most preferably at least 0.9, with at least 70% of the aluminum contained in said peaks.
- the aqueous solution may be obtained by diluting a standard commercially available 50% salt solution with water to the desired concentra- tion, which is preferably 8 to 15%.
- the temperature and time of heating may be adjusted as necessary to achieve the desired degree of conversion to the enhanced state. Generally, longer times are required at lower temperatures. It is preferred to heat above 50°C, more preferably at 70° to 100°C, for at least two hours, more preferably for at least 10 hours or more. Excellent results are obtained by heating at about 80° to 85°C. for about 15 to 20 hours.
- aluminum metal is reacted with aluminum halide, typically aluminum chloride, or with hydrogen halide, typically hydrochloric acid, in water at a temperature of about 50° to 100°C, the concentration of the reactants being such as to provide an aqueous solution of aluminum hydroxy halide, typically aluminum chlorohydrate, of about 8 to 25%, preferably about 10 to about 20%, by weight.
- aluminum halide typically aluminum chloride
- hydrogen halide typically hydrochloric acid
- the antiperspirant salt utilized in step (a) is an aluminum-zirconium salt
- the amount of each salt should be adjusted so that the final solution will have a total salt concentration within the limits specified as desired for step (a) .
- the liquid polyhydric alcohol which utilized in step (b) may be selected from any of those which are generally used in cosmetic compositions and which are liquid at room temperature. These typically include liquid aliphatic alcohols having from 2 to 12 carbon atoms and two or more hydroxyl groups and liquid polyaliphatic ether-polyhydroxy compounds.
- propylene glycol either 1,2- or 1,3-
- butylene glycol diethylene glycol, dipropylene glycol, glycerin, sorbitol
- trimethylol propane 2-methyl-2,4- pentane-diol, 2-ethyl-l,3-hexane-diol
- polyethylene glycols polypropylene glycols and mixtures thereof.
- the preferred liquid polyhydric alcohols are propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, glycerin, sorbitol and mixtures thereof. Most preferred are propylene glycol and sorbitol.
- the liquid polyhydric alcohol may be mixed with the aqueous antiperspirant salt solution at any temperature between about 0°C. and about 100°C, preferably between room temperature and 85°C.
- the amount of polyhydric alcohol (or conversely, the amount of antiperspirant salt solution) should be that amount which will provide, after the evaporation step (c) , the desired concentration of antiperspirant salt in the polyhydric alcohol solution which is recovered.
- the mixed solution is subjected to evaporation conditions in step (c) in order to remove most, but not all, of the unbound water so as to provide a liquid polyhydric alcohol solution containing about 20 to 50%, preferably about 30 to 47%, enhanced efficacy antiperspirant salt and about 2 to 16%, preferably about 4 to 12%, water (unbound as measured by Karl Fischer titration) , with the balance being said polyhydric alcohol.
- the evaporation step should be conducted under such conditions that the enhanced efficacy state of the antiperspirant salt, as evidenced by HPLC peak 4 to peak 3 area ratio, is substantially retained. Thus, it is generally important that the salt not be exposed to high temperature conditions for any significant length of time.
- the evaporation step is preferably conducted under vacuum, typically under 150mm Hg (absolute pressure) , preferably about 5 to about 70mm Hg (absolute pressure) , and at temperatures under 110°C, preferably about 20° to about 85°C.
- the greater the vacuum i.e. the lower the absolute pressure
- the evaporation step may be conducted in any suitable type of vacuum evaporation ⁇ q. pment, the use of a rotary vacuum evaporator or a flash vacuum evaporator is especially preferred.
- the evaporation In this way it is possible to complete the conversion of a given aliquot of solution in under four hours.
- the average residence time of antiperspirant salt in the evaporator should be about three hours or less. The skilled worker should have no difficulty selecting appropriate equipment to carry out the rapid evaporation as described.
- the aqueous salt solution provided in step (a) may be concentrated (for example, in a vacuum evaporator) to about 40 to 50% salt concentration prior to adding the polyhydric alcohol solution in step (b) .
- zirconium salt it may be added either before or preferably after this concentration step. If this procedure is followed, it is most important that steps (b) and (c) are carried out as rapidly as possible so as to avoid any deterioration in peak 4 to peak 3 ratio. This is because the higher concentration salt solution is much more prone to reversion to the non-enhanced state.
- an aqueous zirconium salt solution in an amount to provide the requisite Al:Zr ratio either (i) to the mixed solution after the liquid polyhydric alcohol has been added in accordance with step (b) or (ii) to the liquid polyhydric alcohol before it is added in accordance with step (b) .
- the zirconium salt can be added at any stage prior to the evaporation step (c) .
- the polyhydric alcohol solution of enhanced efficacy antiperspirant salt which is recovered in the process of the present invention will retain substantially the same degree of enhanced efficacy in the salt as was there when the salt was prepared. That is, the enhanced efficacy salt, when reconstituted as a 10% aqueous solution, should produce an HPLC chromatogram (as described, for example, in US 5,330,751) wherein at least 70%, preferably at least 80%, of the aluminum is contained in two successive peaks, conveniently labeled peaks 3 and 4, wherein the ratio of the area under peak 4 to the area under peak 3 is at least 0.5, preferably at least 0.7, and most preferably at least 0.9 or higher.
- HPLC chromatogram as described, for example, in US 5,330,751
- the ratio of the area under peak 4 to the area under peak 3 is at least 0.5, preferably at least 0.7, and most preferably at least 0.9 or higher.
- the 10% aqueous salt solution which is subjected to chromatographic analysis may be prepared either by diluting the polyhydric alcohol solution with sufficient water to form a 10% aqueous salt solution or by precipitating the salt from the polyhydric alcohol by addition of acetone, then redis- solving the salt in water at a concentration of 10%.
- the method of the present invention is particularly advantageous for the preparation of polyhydric alcohol solutions of enhanced efficacy aluminum-zirconium antiperspirant salts, preferably aluminum-zirconium chlorohydrate salts, containing higher levels of glycinate salts, such as sodium or zinc glycinate, which increases the pH of the antiperspirant.
- aluminum-zirconium antiperspirant salts preferably aluminum-zirconium chlorohydrate salts, containing higher levels of glycinate salts, such as sodium or zinc glycinate, which increases the pH of the antiperspirant.
- the pH of the recovered solution (when measured after addition of an equal part of distilled water) will fall within the range of about 4.1 to 5.0, preferably about 4.4 to 5.0, when a sufficient amount of additional alkaline glycinate salt is added during the process, typically an amount sufficient to bring the total Gly:Zr ratio to about 1.3 or higher, preferably about 1.5:1 to about 4:1, more preferably about 1.5:1 to about 3:1.
- alkaline glycinate salt is meant any metal glycinate salt which is soluble in polyhydric alcohol and water and which partially neutralizes the acidity of the antiperspirant salt without otherwise causing any reduction in clarity of the final product.
- Preferred alkaline glycinates are sodium, potassium and zinc glycinate.
- an aqueous solution of alkaline glycinate such as 50% sodium glycinate
- the polyhydric alcohol typically propylene glycol
- an aqueous solution of zirconium hydroxychloride glycinate typically a 50% solution with GlytZr ratio about 1:1
- an aqueous solution of enhanced efficacy aluminum chlorohydrate typically 10% ACH'
- This solution is then subjected to vacuum evaporation as previously described to remove most of the water, providing a polyhydric alcohol solution containing about 20 to 50% by weight aluminum-zirconium chlorohydrate glycinate (Gly:Zr ratio of about 1.5:1 to 4:1), and 2 to 16% water, with a pH between about 4.1 and 5.0 when diluted with an equal portion of water.
- a polyhydric alcohol solution containing about 20 to 50% by weight aluminum-zirconium chlorohydrate glycinate (Gly:Zr ratio of about 1.5:1 to 4:1), and 2 to 16% water, with a pH between about 4.1 and 5.0 when diluted with an equal portion of water.
- weight percent of antiperspirant salt is intended to be calculated as weight percent of the salt excluding bound water and glycine or glycinate in accordance with the conventional industry standard method.
- calculation of anti ⁇ perspirant salt weight percent in accordance with the standard method compares with the new U.S.P. calculation as follows:
- ACH enhanced efficacy salt solution
- EXAMPLE 2 To 241 lbs. (109.4 kg) 10% ACH' solution (prepared as in Example 1) was added 32 lbs. (14.5 kg) ZHC-gly solution (50%), then 129 lbs. (58.6 kg) propylene glycol. The combined solution was preheated to 70-75°C. and continuously fed at about 3-4 gals/hr into a type JHE flash evaporator (APV Crepaco Inc.,
- the average residence time of an aliquot of solution in the evaporator was about 3 hours.
- a 50% sodium glycinate solution was prepared by mixing 171 lbs. (77.6 kg) 50% NaOH with 67.8 lbs. (30.8 kg) water, then adding 160.3 lbs. (72.8 kg) of glycine (1:1 mole ratio of glycine to NaOH) , the temperature rising from 25° to 30°C, then from 30° to 35 ⁇ C, after the first and second additions respectively.
- To 103.3 lbs. (46.9kg) of propylene glycol was added 7.8 lbs. (3.5kg) of 50% sodium glycinate and the solution mixed for ten minutes. To this solution was added 33.9 lbs.
- a clear solution comprising 65% propylene glycol, 35% enhanced efficacy aluminum-zirconiu - tetrachlorohydrex-glycine (more than 80% of aluminum in peaks 3 and 4 with peak 4 to peak 3 area ratio greater than 1 and Gly:Zr ratio about 1.6:1), and 5% water.
- the pH of a sample of this solution diluted with an equal portion of distilled water was about 4.7.
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Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002204015A CA2204015C (en) | 1994-11-02 | 1995-10-30 | Method of making polyhydric alcohol solutions of enhanced efficacy antiperspirant actives |
JP8515380A JPH10509142A (en) | 1994-11-02 | 1995-10-30 | Method for preparing polyhydric alcohol solution of antiperspirant active substance with enhanced efficacy |
NZ296385A NZ296385A (en) | 1994-11-02 | 1995-10-30 | Method of preparing aluminium antiperspirant salt in polyhydric alcohol solutions |
BR9509571A BR9509571A (en) | 1994-11-02 | 1995-10-30 | Process of preparing a solution in a polyhydric alcohol of an aluminum salt and an aluminum antiperspirant antiperspirant with improved efficacy and product |
DE69512430T DE69512430T2 (en) | 1994-11-02 | 1995-10-30 | MANUFACTURING METHOD OF SOLUTIONS OF MULTI-VALUE ALCOHOLS CONTAINING ANTI-SWEATHANT AGENTS, WITH IMPROVED EFFECTIVENESS |
EP95939000A EP0789554B1 (en) | 1994-11-02 | 1995-10-30 | Method of making polyhydric alcohol solutions of enhanced efficacy antiperspirant actives |
AU40179/95A AU688630B2 (en) | 1994-11-02 | 1995-10-30 | Method of making polyhydric alcohol solutions of enhanced efficacy antiperspirant actives |
MXPA/A/1997/003189A MXPA97003189A (en) | 1994-11-02 | 1997-04-30 | Method for manufacturing solutions of polyhydrical alcohols with antitranspirant active compounds with better efficiency |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US33389694A | 1994-11-02 | 1994-11-02 | |
US333,896 | 1994-11-02 | ||
US397,451 | 1995-03-02 | ||
US08/397,451 US5643558A (en) | 1994-11-02 | 1995-03-02 | Method of making polyhydric alcohol solutions of enhanced efficacy antiperspirant actives |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1996014052A1 true WO1996014052A1 (en) | 1996-05-17 |
Family
ID=26988944
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1995/014073 WO1996014052A1 (en) | 1994-11-02 | 1995-10-30 | Method of making polyhydric alcohol solutions of enhanced efficacy antiperspirant actives |
Country Status (11)
Country | Link |
---|---|
US (1) | US5939057A (en) |
EP (1) | EP0789554B1 (en) |
JP (1) | JPH10509142A (en) |
CN (1) | CN1167434A (en) |
AT (1) | ATE184784T1 (en) |
AU (1) | AU688630B2 (en) |
CA (1) | CA2204015C (en) |
DE (1) | DE69512430T2 (en) |
ES (1) | ES2138242T3 (en) |
NZ (1) | NZ296385A (en) |
WO (1) | WO1996014052A1 (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1998058626A1 (en) * | 1997-06-25 | 1998-12-30 | The Gillette Company | Polyhydric alcohol stabilized antiperspirant salt solutions |
WO1999021528A3 (en) * | 1997-10-29 | 1999-08-26 | Colgate Palmolive Co | Stabilized aluminium zirconium antiperspirant compositions |
WO2000048564A1 (en) * | 1999-02-18 | 2000-08-24 | The Procter & Gamble Company | Process of making zirconium-aluminum antiperspirant active |
WO2001013870A3 (en) * | 1999-08-24 | 2001-09-20 | Procter & Gamble | Process for making anhydrous compositions containing solubilized, enhanced antiperspirant active |
WO2002034211A3 (en) * | 2000-10-20 | 2003-07-31 | Colgate Palmolive Co | Antiperspirant salts for enhanced cosmetic products |
WO2007004163A1 (en) * | 2005-06-30 | 2007-01-11 | The Gillette Company | Particulate enhanced efficacy antiperspirant salt with raised ph |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6042816A (en) * | 1998-08-19 | 2000-03-28 | The Gillette Company | Enhanced antiperspirant salts stabilized with calcium and concentrated aqueous solutions of such salts |
US6451296B1 (en) * | 2000-02-01 | 2002-09-17 | Zijun Li | Enhanced efficacy aluminum-zirconium antiperspirants and methods for making |
US6960338B2 (en) * | 2002-06-28 | 2005-11-01 | Reheis, Inc. | Amino acid free stable aluminum/zirconium antiperspirant solution |
US6649153B1 (en) | 2002-09-16 | 2003-11-18 | Reheis Inc. | Skin friendly antiperspirant composition and method of making |
US7153495B2 (en) * | 2004-06-10 | 2006-12-26 | Reheis, Inc. | Fragrance friendly and cost effective antiperspirant actives and method of making the same |
KR100635698B1 (en) * | 2005-05-24 | 2006-10-17 | 한국전력공사 | Method for separating acid gas from mixed gas and absorbent for acid gas separation in mixed gas |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1486857A (en) * | 1965-07-16 | 1967-06-30 | Armour Pharma | Complexes soluble in alcohols, process for their preparation, and preparations using them, as well as process for their preparation |
US3359169A (en) * | 1962-04-27 | 1967-12-19 | Revlon | Aluminum compounds |
US3420932A (en) * | 1966-12-20 | 1969-01-07 | Armour Pharma | Methods of making alcohol soluble complexes of aluminum and preparations employing the complexes |
EP0007191A1 (en) * | 1978-06-23 | 1980-01-23 | Unilever Plc | Antiperspirant basic aluminium chloride/polyhydroxy compound complex |
US4781917A (en) * | 1987-06-26 | 1988-11-01 | The Proctor & Gamble Company | Antiperspirant gel stick |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3405153A (en) * | 1965-09-15 | 1968-10-08 | Armour Pharma | Metal-aluminum inorganic-organic complexes and methods of preparing same |
US3947556A (en) * | 1971-07-20 | 1976-03-30 | Armour Pharmaceutical Company | Zinc complexes of basic aluminum chlorides and methods of making same |
US3981986A (en) * | 1973-11-23 | 1976-09-21 | Armour Pharmaceutical Company | Zirconium-aluminum-polyol buffered anti-perspirant complexes |
US5234677A (en) * | 1984-11-21 | 1993-08-10 | Reheis Inc. | Enhanced efficacy aluminum chlorhydrate antiperspirant and method of making same |
EP0295070A3 (en) * | 1987-06-11 | 1989-05-31 | The Procter & Gamble Company | Liquid antiperspirant actives and processes for preparing the same |
EP0404533A1 (en) * | 1989-06-23 | 1990-12-27 | The Procter & Gamble Company | Liquid solubilized antiperspirant actives and processes for preparing the same |
US5463098A (en) * | 1992-11-16 | 1995-10-31 | Giovanniello; Rocco | Clear antiperspirant gel stick and method for making same |
-
1995
- 1995-10-30 DE DE69512430T patent/DE69512430T2/en not_active Expired - Fee Related
- 1995-10-30 AT AT95939000T patent/ATE184784T1/en active
- 1995-10-30 NZ NZ296385A patent/NZ296385A/en unknown
- 1995-10-30 AU AU40179/95A patent/AU688630B2/en not_active Ceased
- 1995-10-30 ES ES95939000T patent/ES2138242T3/en not_active Expired - Lifetime
- 1995-10-30 EP EP95939000A patent/EP0789554B1/en not_active Expired - Lifetime
- 1995-10-30 WO PCT/US1995/014073 patent/WO1996014052A1/en active IP Right Grant
- 1995-10-30 JP JP8515380A patent/JPH10509142A/en active Pending
- 1995-10-30 CN CN95196528.XA patent/CN1167434A/en active Pending
- 1995-10-30 CA CA002204015A patent/CA2204015C/en not_active Expired - Fee Related
-
1997
- 1997-06-13 US US08/874,232 patent/US5939057A/en not_active Expired - Lifetime
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3359169A (en) * | 1962-04-27 | 1967-12-19 | Revlon | Aluminum compounds |
FR1486857A (en) * | 1965-07-16 | 1967-06-30 | Armour Pharma | Complexes soluble in alcohols, process for their preparation, and preparations using them, as well as process for their preparation |
US3420932A (en) * | 1966-12-20 | 1969-01-07 | Armour Pharma | Methods of making alcohol soluble complexes of aluminum and preparations employing the complexes |
EP0007191A1 (en) * | 1978-06-23 | 1980-01-23 | Unilever Plc | Antiperspirant basic aluminium chloride/polyhydroxy compound complex |
US4781917A (en) * | 1987-06-26 | 1988-11-01 | The Proctor & Gamble Company | Antiperspirant gel stick |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1998058626A1 (en) * | 1997-06-25 | 1998-12-30 | The Gillette Company | Polyhydric alcohol stabilized antiperspirant salt solutions |
WO1999021528A3 (en) * | 1997-10-29 | 1999-08-26 | Colgate Palmolive Co | Stabilized aluminium zirconium antiperspirant compositions |
AU745523B2 (en) * | 1997-10-29 | 2002-03-21 | Colgate-Palmolive Company, The | Improved antiperspirant actives and formulations made therefrom |
EP1464329A3 (en) * | 1997-10-29 | 2004-11-17 | Colgate-Palmolive Company | Antiperspirant actives and formulations made therefrom |
CZ301082B6 (en) * | 1997-10-29 | 2009-10-29 | Colgate-Palmolive Company | Stabilization process of aluminium zirconium composition containing aqueous component |
WO2000048564A1 (en) * | 1999-02-18 | 2000-08-24 | The Procter & Gamble Company | Process of making zirconium-aluminum antiperspirant active |
WO2001013870A3 (en) * | 1999-08-24 | 2001-09-20 | Procter & Gamble | Process for making anhydrous compositions containing solubilized, enhanced antiperspirant active |
WO2002034211A3 (en) * | 2000-10-20 | 2003-07-31 | Colgate Palmolive Co | Antiperspirant salts for enhanced cosmetic products |
WO2007004163A1 (en) * | 2005-06-30 | 2007-01-11 | The Gillette Company | Particulate enhanced efficacy antiperspirant salt with raised ph |
Also Published As
Publication number | Publication date |
---|---|
NZ296385A (en) | 1999-04-29 |
CA2204015C (en) | 2001-02-06 |
DE69512430T2 (en) | 2000-03-16 |
MX9703189A (en) | 1997-07-31 |
JPH10509142A (en) | 1998-09-08 |
CN1167434A (en) | 1997-12-10 |
CA2204015A1 (en) | 1996-05-17 |
ATE184784T1 (en) | 1999-10-15 |
ES2138242T3 (en) | 2000-01-01 |
EP0789554B1 (en) | 1999-09-22 |
AU4017995A (en) | 1996-05-31 |
DE69512430D1 (en) | 1999-10-28 |
AU688630B2 (en) | 1998-03-12 |
US5939057A (en) | 1999-08-17 |
EP0789554A1 (en) | 1997-08-20 |
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